CN114345359B - Preparation method and application of catalyst for efficient catalytic pyrolysis of sludge pyrolysis tar and real-time detection system - Google Patents

Preparation method and application of catalyst for efficient catalytic pyrolysis of sludge pyrolysis tar and real-time detection system Download PDF

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CN114345359B
CN114345359B CN202111661041.1A CN202111661041A CN114345359B CN 114345359 B CN114345359 B CN 114345359B CN 202111661041 A CN202111661041 A CN 202111661041A CN 114345359 B CN114345359 B CN 114345359B
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sludge
gas
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CN114345359A (en
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张军
金厚宇
尹琳琳
陈正瑞
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Harbin Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract

The invention discloses a preparation method and application of a catalyst for efficient catalytic pyrolysis of sludge pyrolysis tar and a real-time detection system, and belongs to the technical field of preparation and catalysis of perovskite catalysts. According to the invention, the catalyst of Ni and Co bimetallic oxides loaded on the surface of the perovskite type oxide carrier is prepared by adopting a twice sol-gel method, metal ions are loaded in the carrier by utilizing the limiting effect of the perovskite type oxide, and meanwhile, oxygen anions in the catalyst react with surface carbon, so that the influence of active metal sintering and surface carbon covering active sites of the catalyst on the catalytic activity of the catalyst can be effectively reduced, and the deactivation resistance of the catalyst is improved. According to the invention, the pyrolysis tar detection system is constructed, and the detection system can realize online detection of pyrolysis tar generated in any period, so that the content information of each component in the pyrolysis tar is accurately analyzed in real time, and the real-time detection of the substance components and the content in the sludge pyrolysis gasification tar is realized.

Description

Preparation method and application of catalyst for efficient catalytic pyrolysis of sludge pyrolysis tar and real-time detection system
Technical Field
The invention relates to a preparation method and application of a catalyst for efficient catalytic pyrolysis of sludge pyrolysis tar and a real-time detection system, and belongs to the technical field of preparation and catalysis of perovskite type catalysts.
Background
The sludge has rich organic matter content, and the chemical energy of the organic matter can be efficiently converted into fuel gas through pyrolysis and gasification treatment, and then the cogeneration power generation is considered as an effective way for solving the current sludge treatment and safety disposal problems. However, the sludge pyrolyzes the fuel gas and simultaneously produces tar and impurities such as intermediate products, solid particles, nitrogen sulfide and the like, wherein the tar content accounts for more than 80% of the total amount of the impurities. The tar pollutes the environment, blocks the pipeline, corrodes the equipment, reduces the biomass gasification energy conversion rate, and endangers the human health. Therefore, tar removal in fuel gas is a long-term difficult problem faced by the development of a sludge pyrolysis gasification technology.
In various tar treatment methods, the catalytic cracking method can greatly reduce the tar conversion temperature by reducing the reaction activation energy under the action of a proper catalyst, and meanwhile, the catalytic reforming of the tar into small-molecule fuel gas is a tar in-situ removal technology with great development potential.
However, the existing tar in-situ catalytic cracking technology mainly has two problems in the practical engineering application process: the method has the advantages of high efficiency, high catalytic capability and good pollution resistance, and no method for detecting the secondary products of the catalyst and tar in the catalytic pyrolysis process in real time. At present, a nickel-based catalyst is known to have good tar catalytic cracking efficiency, but in the application process, the nickel metal is found to be deactivated due to the rapid reduction of catalytic sites on the metal surface, which is easily caused by carbon deposit coverage and grain aggregation, so that the catalytic efficiency is rapidly reduced. Therefore, it is necessary to provide a catalyst capable of improving the catalyst activity and of limiting the sintering and carbon deposit coverage of the catalytic metal crystallites.
Meanwhile, as the catalyst for pyrolysis of tar still has the defect of catalyst deactivation, in order to better characterize the efficiency of the catalyst in the catalytic pyrolysis process of tar, the problem of real-time detection of the components and concentration of tar also needs to be solved, data support is provided for the regeneration and periodic replacement of the catalyst, and the stable quality of a gas product obtained by pyrolysis gasification can be ensured. The existing tar detection technology mainly carries out offline analysis on collected pyrolysis tar tail gas on a laboratory detection instrument, and the method can obtain the composition and content of tar pyrolysis gasification products, but has the defects of higher cost of required manpower and material resources, longer consumption time, incapability of obtaining real-time gasification product data and difficulty in popularization and application to large-scale engineering. Therefore, it is also necessary to provide a real-time detection system for tar products that provides data support for catalyst regeneration and periodic replacement.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides the high-efficiency sludge pyrolysis tar catalytic cracking catalyst which has high tar catalytic efficiency, strong inactivation resistance and stable and controllable catalyst preparation method and performance, and constructs a real-time detection system capable of quantitatively analyzing the components and the content of the sludge catalytic pyrolysis tar.
The technical scheme of the invention is as follows:
The preparation method of the catalyst for high-efficiency catalytic pyrolysis of the sludge pyrolysis tar comprises the following steps:
Step 1, preparing a perovskite type oxide carrier by adopting a sol-gel method;
And 2, loading nickel-cobalt binary metal on a perovskite type oxide carrier by adopting a sol-gel method to obtain the catalyst for high-efficiency catalytic pyrolysis of the sludge pyrolysis tar.
Further defined, the operation of step 1 is as follows:
Lanthanum nitrate, strontium nitrate and aluminum nitrate are mixed uniformly, citric acid and ethylene glycol are added to form a perovskite oxide precursor, and the perovskite oxide precursor is dried, ground and calcined to form the perovskite oxide carrier.
Further defined, in step 1, the mass ratio of lanthanum nitrate, strontium nitrate and aluminum nitrate is (8.08-10.39): (0.57-1.69): 10.
Still further defined, the ratio of the total molar amount of lanthanum nitrate, strontium nitrate and aluminum nitrate to the molar amount of citric acid and the molar amount of ethylene glycol in step1 is 1:2: (1-3).
Further defined, the drying process conditions in step 1 are: the temperature is 85 ℃ and the time is 12 hours.
Further defined, the calcination treatment conditions in step 1 are: the temperature is 900 ℃ and the time is 4 hours.
Further defined, the operation of step 2 is as follows:
And (2) uniformly mixing the perovskite oxide carrier prepared in the step (1), nickel nitrate and cobalt nitrate, adding citric acid and ethylene glycol to form a perovskite oxide precursor, drying, grinding, and calcining to form the catalyst.
Further defined, in step 2, the mass ratio of nickel nitrate, cobalt nitrate and perovskite oxide precursor is (3.16 to 6.33): (1.09-3.29): 10.
Still further defined, the ratio of the total molar amount of nickel nitrate, cobalt nitrate, and perovskite oxide precursor to the molar amount of citric acid and the molar amount of ethylene glycol is 1:2: (1-3).
Further defined, the drying process conditions in step 2 are: the temperature is 85 ℃ and the time is 12 hours.
Further defined, the calcination treatment conditions in step 2 are: the temperature is 900 ℃ and the time is 4-6 h.
The method for efficiently catalyzing and cracking the pyrolysis tar by using the catalyst comprises the following steps:
step one, mixing sludge pyrolysis tar and a perovskite oxide catalyst, and carrying out catalytic cracking reaction at 700-800 ℃ to generate pyrolysis tar;
And step two, introducing the pyrolysis tar generated in the step one into a real-time pyrolysis tar detection system, and detecting and analyzing the components and the content of the pyrolysis tar in real time.
Further defined, the specific operation process of the first step is as follows:
Adding sludge pyrolysis tar into an upper pipe section of a two-section fixed bed reactor, adding a perovskite oxide catalyst into a lower pipe section, then raising the temperature of the lower pipe section to 700 ℃ at a heating rate of 30 ℃/min, then introducing H 2 into the system at a flow rate of 100mL/min, stopping introducing H 2 after lasting 30min, introducing N 2 into the system at a flow rate of 500mL/min for 5min, finally switching the introducing rate of N 2 to 100mL/min, controlling the heating rate of the upper pipe section to 300 ℃ at a heating rate of 30 ℃/min, gasifying sludge tar, and performing catalytic cracking reaction to generate pyrolysis gas.
The pyrolysis tar real-time detection system comprises a smoke filter, a dryer, a gas heat preservation tank, a GC-MS detection system, a pyrolysis tar condensing system and a gas collecting system, wherein pyrolysis gas generated by the two-stage fixed bed reactor is treated by the smoke filter, the dryer and the gas heat preservation tank in sequence, and then is controlled by a valve, part of the pyrolysis gas enters the GC-MS detection system, and the other part of the pyrolysis gas is collected by the gas collecting system after passing through the pyrolysis tar condensing system.
Further defined, the GC-MS detection system comprises an on-line gas chromatography-mass spectrometry system and a computer digital display system, wherein the on-line gas chromatography-mass spectrometry system comprises a gas source system for generating H 2 and He, a gas chromatography and mass spectrometry detector and a sample collection aspiration pump.
Further defined, the soot filter employs ceramic membrane physical filtration.
Further defined, the gas drying pool is a U-shaped pipe for placing calcium chloride or allochroic silica gel.
Further limited, the gas heat preservation tank is used for preserving the heat of the pyrolysis tar, so that the pyrolysis tar is maintained at the temperature of not lower than 300 ℃ (300-400 ℃).
Further defined, the pyrolysis tar condensing system is composed of two stages of ice water bath n-hexane solvent in series.
Further defined, the gas collection system includes a gas flow detector for measuring the real-time flow of pyrolysis tar and calculating an accumulated flow, and a gas bag.
The invention has the beneficial effects that:
(1) According to the invention, the catalyst of Ni and Co bimetallic oxides loaded on the surface of the perovskite type oxide carrier is prepared by adopting a twice sol-gel method, metal ions are loaded in the carrier by utilizing the limiting effect of the perovskite type oxide, and meanwhile, oxygen anions in the catalyst react with surface carbon, so that the influence of active metal sintering and surface carbon covering active sites of the catalyst on the catalytic activity of the catalyst can be effectively reduced, and the deactivation resistance of the catalyst is improved.
(2) The invention utilizes the property of perovskite oxide mixed ion-electron conductor, can conduct oxygen anion and electron conduction at the same time, greatly increases the number of catalytic active sites and reaction interfaces, effectively improves the catalytic activity and carbon deposition resistance of the catalyst, has higher catalytic cracking performance on tar, has a tar conversion rate of more than 80%, reduces the species in the sludge tar pyrolysis gas after reaction, increases the content of small molecular compounds, and effectively improves the quality of the sludge tar pyrolysis gas. In addition, the synergistic effect of Ni-Co bimetallic can also improve the catalytic activity and service life of the catalyst.
(3) The catalyst activation process provided by the invention is to reduce the Ni and Co bimetallic oxides loaded on the surface of the perovskite carrier into an elemental form under the action of high-temperature H 2/N2 atmosphere, while the perovskite oxide carrier composed of La, sr and Al can keep stable structure under the condition, the original perovskite oxide structure is not destroyed, and the catalytic active component is mainly reduced Ni-Co bimetallic.
(4) The perovskite precursor is prepared by adopting a sol-gel method, the sol-gel method is relatively simple, the cost is low, meanwhile, the synthesized oxide has a stable crystal structure, good lattice oxygen activity and high specific surface area of the catalyst, and a certain proportion of ethylene glycol is added in the preparation process to promote the formation of uniform and stable gel in the preparation process, meanwhile, the acuteness of the decomposition process of the gel in the calcination process is reduced, and the condition that the citric acid gel expands due to heating and overflows the material waste of a reaction carrier can be prevented. Meanwhile, evaporating and drying at 85 ℃, concentrating the precursor liquid into uniform wet gel, and drying to form foam solid, so that a perovskite oxide precursor with less impurities and stable components can be obtained, and a stable perovskite oxide carrier of La xSr1-xAlO3 can be obtained after calcination, wherein Sr is a common perovskite A-site dopant, so that the perovskite carrier can obtain more active sites and lattice oxygen, and the catalytic activity and the anti-carbon property are improved.
(5) According to the invention, the Ni and Co bimetallic is loaded on the La xSr1-xAlO3 perovskite oxide carrier by adopting a sol-gel method, and the synergistic effect of the Ni-Co bimetallic can effectively improve the sintering resistance of the catalyst active metal at high temperature. The sol-gel method can make the metal more tightly bonded to the support than the impregnation method. Under the action of a sol-gel method, ni 2+、Co2+ can be combined with excessive A-site metal La 3+ or Sr 2+ in a perovskite oxide carrier and introduced into a perovskite structure, so that the active site and lattice oxygen content of the catalyst can be further improved; in addition, the content of La and Sr elements on the surface of the catalyst is higher than that of the catalyst by an impregnation method, the Sr elements provide an alkaline environment for the catalyst, and the carbon deposition on the surface of the catalyst is inhibited by enhancing the reaction of moisture adsorption and carbon deposition at high temperature, so that the carbon deposition resistance of the catalyst is improved.
(6) In order to better characterize the efficiency of the catalyst in the tar catalytic pyrolysis process, the invention constructs a pyrolysis tar real-time detection system, the detection system can realize real-time detection of pyrolysis tar and content generated in any period, solid particles and vapor of the pyrolysis tar are removed from the pyrolysis tar generated by the two-stage fixed bed reactor through the smoke filter and the gas dryer, the interference of impurities in the pyrolysis tar on the detection system is reduced, the clean dry pyrolysis tar enters a gas chromatography-mass spectrometry combined detection system under the action of an air pump for qualitative and quantitative analysis, and the real-time and accurate analysis of content information of each component in the pyrolysis tar, such as the concentration of benzene, toluene, xylene, naphthalene, oleamide and the like, is realized, and the real-time detection of the content of substance components in the sludge pyrolysis gasification tar is realized.
Drawings
FIG. 1 is a schematic diagram of a sludge pyrolysis reaction platform and a real-time tar product detection device.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
Example 1:
The preparation method of the catalyst comprises the following steps:
(1) 3.464g of lanthanum nitrate, 0.4233g of strontium nitrate and 3.751g of aluminum nitrate are placed in a beaker, mixed and dissolved in deionized water, 8.406g of citric acid and 3.34mL of ethylene glycol are added into the system, stirred until the mixture is completely dissolved, a rotor is placed into the system, stirred for 12 hours under the action of a magnetic stirrer, and then dried in an oven at 85 ℃ for 12 hours, so that the perovskite oxide precursor is obtained. Grinding the precursor, placing the ground precursor into a quartz boat, and calcining the ground precursor at 900 ℃ for 4 hours to obtain perovskite type oxide carrier powder.
(2) 0.7907G of nickel nitrate and 0.3288g of cobalt nitrate are dissolved in water, then 1.618g of citric acid is added and stirred until the nickel nitrate and the cobalt nitrate are completely dissolved, 1.5g of perovskite oxide carrier powder prepared in the step one is added into a system, a rotor is placed into the system and stirred for 12 hours under the action of a magnetic stirrer, and then the mixture is dried for 12 hours in an oven at 85 ℃ to obtain the novel catalyst precursor. And grinding the precursor, placing the ground precursor into a quartz boat, and calcining the ground precursor at 800 ℃ for 4 hours to obtain the novel catalyst powder. Grinding the novel catalyst powder to 60-100 meshes for standby.
The prepared catalyst is used in efficient catalytic pyrolysis of sludge pyrolysis tar, a specific experimental device is shown in figure 1, the experimental device comprises a two-stage fixed bed reactor 1, a temperature control device 2, an air supply system 3, a standard substance injection port 4, a two-stage reaction heating furnace 5, a smoke filter 7, a gas dryer 8, a gas heat preservation tank 9, a sampling valve 10, an on-line gas chromatography-mass spectrometry detection system 11, a carrier gas system 12, an air pump 13, a computer 14, a condensing and absorbing system 15, a gas flowmeter 16 and a gas collecting bag 17, wherein the hearth material of the two-stage fixed bed reactor 1 is polycrystalline alumina refractory material, the maximum temperature can reach 1200 ℃, the two-stage quartz tube with the specification of 750mm and the tube diameter of 30mm is placed in the heating furnace, the high-temperature use of 1200 ℃ can be born, the gas supply system 3 consists of an N 2 gas cylinder, a hydrogen generator, a gas flow rate controller and a gas passage, wherein the volume purity of N 2 in the N 2 gas cylinder is more than 99.9%, the generation rate of H 2 of the hydrogen generator is at most 500mL/min, the volume purity of H 2 is more than 99.9%, the gas flow rate controller controls the gas flow rate to change in 0-500 mL/min, the smoke filter 7 mainly adopts a ceramic membrane physical filtration method, the gas dryer 8 is a U-shaped pipe for placing calcium chloride or allochroic silica gel, the gas heat preservation tank 9 is used for preserving pyrolysis tar, the pyrolysis tar is maintained at a temperature of not lower than 300 ℃ (kept at 300-400 ℃), the condensation and absorption system 15 consists of two-stage ice water bath N-hexane, the gas flowmeter 16 can measure real-time flow rate of noncondensable gas and calculate accumulated flow rate, and finally the generated noncondensable gas is collected for standby through the gas collecting bag 17.
When the device works, sludge tar and a catalyst are respectively placed on a quartz sand gasket 6 at the upper section and a quartz sand gasket 6 at the lower section of the two-section fixed bed reactor 1, a temperature control device 2 and a gas supply system 3 are regulated, a reserved standard substance sample inlet 4 is closed, a carrier gas system 12 for gas chromatography-mass spectrometry is started, a two-section reaction heating furnace 5 is started, the sludge tar is heated and gasified in a two-section pyrolysis reaction platform, pyrolysis tar is generated after the catalytic pyrolysis of the catalyst on the lower section of the quartz sand gasket 6, sample gas is filtered by a smoke filter 7, then water vapor is removed by a gas dryer 8, the temperature of the pyrolysis tar is kept at 300 ℃ by a gas heat preservation tank 9, then a gas chromatography-mass spectrometry gas detection sampling valve 10 is started, a sucking pump 13 and partial gas samples enter an online gas chromatography-mass spectrometry detection system 11, the pyrolysis tar is separated by a chromatographic column in the gas chromatography-mass spectrometry detection system 11, kurtosis signals with different intensities are generated, gas component information is obtained in a mass spectrometer, and real-time components and content data of the pyrolysis tar are displayed in a computer 14. The rest of the pyrolysis tar passes through a two-stage ice water bath n-hexane absorption system 15, tar components in the pyrolysis tar are collected, and a gas flowmeter 16 and a gas collecting bag 17 store noncondensable gas in the pyrolysis tar.
The method for detecting pyrolysis tar in real time by a detection system comprises the following steps:
Firstly, the components of pyrolysis tar are subjected to component analysis to obtain substances with relatively high content in the tar, including substances such as benzene, toluene, xylene, naphthalene, oleamide and the like, and the mass fractions of the substances in the tar, and the substances are stored in a computer system.
And then, inputting pyrolysis tar into a sludge pyrolysis system, judging the composition of substances in the tar according to a mass spectrogram, comparing the peak area of the pyrolysis tar with that of a standard substance to obtain the concentration of a corresponding compound, and determining the concentration of tar gas according to the calibrated concentration of the compound.
In the embodiment, toluene gas is taken as an example for illustration, samples of standard toluene gas with different concentrations enter a detection system through a reactor, corresponding characteristic spectral lines are output, and a standard curve function of toluene is made according to the peak area of each group of toluene standard substances and the concentration of toluene. The toluene standard peak area and the corresponding toluene concentration data are shown in Table 1 below;
Toluene concentration (vol%) Peak area of corresponding characteristic spectral line
0.2 6.70735
0.4 15.36752
0.8 29.02832
2 73.1144
4 135.02573
According to the data in table 1, the function of toluene concentration x and the corresponding standard peak area y of toluene was found by data fitting to be y=33.714x+1.9521.
Then, the gas to be detected is input into a detection system, and the retention time of the characteristic spectral line and the standard characteristic spectral line of toluene is compared, so that the characteristic spectral line has a spectral peak with the same retention time as the standard characteristic spectral line of toluene, and the toluene contained in the gas to be detected can be determined. And determining the concentration of toluene according to the peak area of the characteristic spectral line and a toluene standard curve function.
When the gas to be detected is input into the detection system, a group of characteristic spectral lines of toluene with peak area of 18.74167 can be obtained, and the concentration of the obtained toluene is 0.498 percent according to the function of the concentration x of the toluene and the peak area y of the standard characteristic spectral line of the corresponding toluene, which is y=33.714x+1.9521. It can be seen that the relative error is 2.4% according to the method of the present invention
When the gas to be detected is input into the detection system, a group of characteristic spectral lines of toluene with peak area of 35.02553 can be obtained, and the concentration of the obtained toluene is 0.981 percent according to the function of the concentration x of the toluene and the peak area y of the corresponding standard characteristic spectral line of the toluene, which is y=33.714x+1.9521. It can be seen that the relative error is 4.0% according to the method of the present embodiment.
When the gas to be detected is input into the detection system, a group of characteristic spectral lines of toluene with the peak area of 73.42578 can be obtained, and the concentration of the obtained toluene is 2.120 percent according to the function of the concentration x of the toluene and the peak area y of the standard characteristic spectral line of the corresponding toluene, which is y=33.714x+1.9521. It can be seen that the relative error is 3.7% according to the method of the present invention.
The result shows that the error between the toluene concentration measured by the detection method provided by the embodiment of the invention and the toluene concentration in the gas to be detected is below 5%, and the measurement result is more accurate.
In the embodiment, a pyrolysis tar sample is taken before catalytic pyrolysis, the composition analysis is carried out on the sludge pyrolysis tar through GC/MS, and the toluene concentration in the pyrolysis tar and the total mass generated by the tar before and after catalytic reaction are compared to obtain that the mass fraction of toluene in the sludge pyrolysis tar is 15%.
The catalytic pyrolysis reaction of this example works as follows:
Adding 0.8g of sludge pyrolysis tar into the upper pipe section of the two-section fixed bed reactor 1, adding 0.8g of perovskite oxide catalyst into the lower pipe section, starting the two-section reaction heating furnace 5 to raise the temperature of the lower pipe section to 700 ℃ at a heating rate of 30 ℃/min, gasifying the sludge tar on the quartz sand gasket 6, controlling the upper pipe section to raise to 300 ℃ at a heating rate of 30 ℃/min, then adjusting a gas flow rate controller to introduce H 2 into the system at a flow rate of 100mL/min, stopping introducing H 2 after the duration of 30min, starting introducing N 2 into the system at a flow rate of 500mL/min for 5min, switching the introducing rate of N 2 to 100mL/min, adding toluene with a concentration of 3.250% (volume fraction) into the system through a toluene feed inlet, introducing toluene into the lower pipe section containing the catalyst along with carrier gas after gasifying the upper pipe section, and starting the catalytic pyrolysis reaction of the sludge tar.
And (3) opening the sampling valve 10, opening the air extracting pump 13, enabling the pyrolysis tar to enter the tar real-time detection device, outputting a characteristic spectral line of toluene in the pyrolysis tar at a computer end to calculate the toluene concentration, and obtaining toluene concentration data of 0.423vol%, wherein the removal rate of the toluene in the reaction system is up to 87%. Finally, the toluene content of the pyrolysis tar is known to be about 15% of the tar, so that the concentration of the tar in the gas to be detected can be obtained by dividing the measured toluene content by 0.15.
The above description is merely a preferred embodiment of the present invention, and since the person skilled in the art can make appropriate changes and modifications to the above-described embodiment, the present invention is not limited to the above-described embodiment, and some modifications and changes of the present invention should fall within the scope of the claims of the present invention.

Claims (6)

1. The preparation method of the catalyst for high-efficiency catalytic pyrolysis of the sludge pyrolysis tar is characterized by comprising the following steps of:
Step 1, preparing a perovskite type oxide carrier by adopting a sol-gel method;
the operation process of the step 1 is as follows:
Uniformly mixing lanthanum nitrate, strontium nitrate and aluminum nitrate, adding citric acid and ethylene glycol to form a perovskite oxide precursor, drying, grinding, and calcining to form a perovskite oxide carrier;
The drying treatment conditions in the step1 are as follows: the temperature is 85 ℃ and the time is 12 hours; the calcining treatment conditions in the step1 are as follows: the temperature is 900 ℃ and the time is 4 hours;
Step 2, loading nickel-cobalt binary metal on a perovskite type oxide carrier by adopting a sol-gel method to obtain a catalyst for high-efficiency catalytic pyrolysis of sludge pyrolysis tar;
the operation process of the step2 is as follows:
Uniformly mixing the perovskite oxide carrier prepared in the step1, nickel nitrate and cobalt nitrate, adding citric acid and ethylene glycol to form a perovskite oxide precursor, drying, grinding, and calcining to form a catalyst;
The drying treatment conditions in the step 2 are as follows: the temperature is 85 ℃ and the time is 12 hours; the calcining treatment conditions in the step 2 are as follows: the temperature is 900 ℃ and the time is 4-6 h.
2. The method for preparing the catalyst for efficient catalytic pyrolysis of sludge pyrolysis tar according to claim 1, wherein the mass ratio of lanthanum nitrate, strontium nitrate and aluminum nitrate in the step 1 is (8.08-10.39): (0.57-1.69): 10; the ratio of the total mole amount of lanthanum nitrate, strontium nitrate and aluminum nitrate to the mole amount of citric acid and the mole amount of ethylene glycol in the step 1 is 1:2: (1-3).
3. The method for preparing the catalyst for efficient catalytic pyrolysis of sludge pyrolysis tar according to claim 1, wherein the mass ratio of nickel nitrate, cobalt nitrate and perovskite oxide precursor in the step 2 is (3.16-6.33): (1.09-3.29): 10; the ratio of the total molar amount of the nickel nitrate, the cobalt nitrate and the perovskite oxide precursor to the molar amount of the citric acid and the molar amount of the ethylene glycol is 1:2: (1-3).
4. A method of using the catalyst of claim 1 for efficient catalytic pyrolysis of sludge pyrolysis tar, the method comprising the steps of:
step one, mixing sludge pyrolysis tar and a perovskite oxide catalyst, and carrying out catalytic cracking reaction at 700-800 ℃ to generate pyrolysis gas;
And step two, introducing pyrolysis gas generated in the step one into a pyrolysis tar real-time detection system, and detecting and analyzing the components and the content of the pyrolysis tar in real time.
5. The method for high-efficiency catalytic pyrolysis of sludge pyrolysis tar by using the catalyst according to claim 4, wherein the specific operation process of the first step is as follows:
Adding sludge pyrolysis tar into an upper pipe section of a two-section fixed bed reactor, adding a perovskite oxide catalyst into a lower pipe section, then raising the temperature of the lower pipe section to 700 ℃ at a heating rate of 30 ℃/min, then introducing H 2 into the system at a flow rate of 100mL/min, stopping introducing H 2 after lasting 30min, introducing N 2 into the system at a flow rate of 500mL/min for 5min, finally switching the introducing rate of N 2 to 100mL/min, controlling the heating rate of the upper pipe section to 300 ℃ at a heating rate of 30 ℃/min, gasifying sludge tar, and performing catalytic cracking reaction to generate pyrolysis gas.
6. The method for high-efficiency catalytic pyrolysis of sludge pyrolysis tar by using the catalyst according to claim 4, wherein the pyrolysis tar real-time detection system in the second step comprises a smoke filter, a dryer, a gas heat preservation tank, a GC-MS detection system, a pyrolysis tar condensation system and a gas collection system, pyrolysis gas generated by the two-stage fixed bed reactor is treated by the smoke filter, the dryer and the gas heat preservation tank in sequence, and then is controlled by a valve, part of pyrolysis gas enters the GC-MS detection system, and the other part of pyrolysis gas is collected by the gas collection system after passing through the pyrolysis tar condensation system.
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